Correlation function formula for the intrinsic viscosity of dilute polymer solutions

The correlation function formalism for the intrinsic viscosity of polymers is studied. A controversy concerning the correct force to use in the momentum flux is resolved. It is shown that when the diffusion equation is used in the full configuration space of polymer segments the forces entering the momentum flux are purely mechanical and there is no entropic contribution. A comparison is made with Kirkwood’s theory of viscoelastic behavior. The correlation function expression we advocate is shown to yield the correct high frequency limiting behavior for the case of elastic dumbbells.

[1]  O. Hassager,et al.  Kinetic theory and rheology of bead‐rod models for macromolecular solutions. I. Equilibrium and steady flow properties , 1974 .

[2]  W. Stockmayer,et al.  Dynamic properties of solutions. Models for chain molecule dynamics in dilute solution , 1970 .

[3]  Raymond J. Seeger,et al.  Lectures in Theoretical Physics , 1962 .

[4]  J. Kirkwood,et al.  The Visco‐Elastic Properties of Solutions of Rod‐Like Macromolecules , 1951 .

[5]  H. Kramers The Behavior of Macromolecules in Inhomogeneous Flow , 1946, Master of Modern Physics.

[6]  M. Doi,et al.  Correlation-Function Formula for the Intrinsic Viscosity of Polymer Solutions , 1973 .

[7]  M. Bixon,et al.  Dynamics of polymer molecules in dilute solutions , 1973 .

[8]  H. R. Warner,et al.  Kinetic theory and rheology of dumbbell suspensions with Brownian motion , 1971 .

[9]  J. Erpenbeck,et al.  Statistical Mechanics of Irreversible Processes in Polymer Solutions , 1958 .

[10]  J. Hearst Intrinsic Viscosity of Stiff‐Chain Macromolecules , 1964 .

[11]  H. R. Warner,et al.  Hydrodynamic Interaction Effects in Rigid Dumbbell Suspensions. I. Kinetic Theory , 1971 .

[12]  M. Fixman Classical statistical mechanics of constraints: a theorem and application to polymers. , 1974, Proceedings of the National Academy of Sciences of the United States of America.

[13]  H. Mori Transport, Collective Motion, and Brownian Motion , 1965 .

[14]  J. Kirkwood,et al.  Non-Newtonian Viscoelastic Properties of Rod-Like Macromolecules in Solution , 1956 .

[15]  G. Fraenkel Visco‐Elastic Effect in Solutions of Simple Particles , 1952 .

[16]  J. Kirkwood The general theory of irreversible processes in solutions of macromolecules , 1996 .